Silicone hydrogels based on vinyl carbonate endcapped fluorinated side chain polysiloxanes

ABSTRACT

Vinyl carbonate endcapped polysiloxanes containing a fluorinated side chain are useful as biomaterials, especially hydrogel biomaterials, including contact lens materials.

FIELD OF THE INVENTION

[0001] The present invention relates to novel polymeric compositions andto medical devices made from such materials. The invention furtherparticularly relates to polymers containing vinyl carbonate endcappedpolysiloxanes having at least one polar fluorinated side chain. Themonomers described herein can be used to make “hard” or “soft” contactlenses, intraocular implants, as well as other prostheses, and moreparticularly “soft” hydrogel contact lenses.

BACKGROUND

[0002] In the field of contact lenses, various factors must combine toyield a material that has appropriate characteristics. Oxygenpermeability, wettability, material strength and stability are but a fewof the factors that must be carefully balanced to achieve a useablecontact lens. Since the cornea receives its oxygen supply exclusivelyfrom contact with the atmosphere, good oxygen permeability is a criticalcharacteristic for any contact lens material. Wettability also isimportant in that, if the lens is not sufficiently wettable, it does notremain lubricated and therefore cannot be worn comfortably in the eye.The optimum contact lens would therefore, have both excellent oxygenpermeability, and excellent tear fluid wettability.

[0003] Polysiloxane materials are useful materials for making contactlenses due to, among other properties, their excellent oxygenpermeability. See U.S. Pat. Nos. 4,153,641 and 4,189,546. Howeverpolysiloxanes are generally hydrophobic. Certain hydrophilic functionalgroups may be attached to polysiloxane-containing monomers, orprepolymers to improve their wettability. See U.S. Pat. Nos. 4,260,725and 4,259,467. However, many hydrophilic comonomers are known to beincompatible with the polysiloxane monomers in the monomer mix, andrequire the presence of solubilizers and compatibilizers for the monomermixture properly polymerize. U.S. Pat. Nos. 5,321,108, 5,387,662 and5,539,016 to Kunzler et al. teach fluorosiloxane-containing monomershaving improved solubility in solvents such as N-vinyl pyrrolidone andN,N-dimethyl acrylamide.

[0004] In addition to oxygen permeability, wettability and compatibilityrequirements, contact lens materials must resist deposits. Somepolysiloxane materials tend to accumulate deposits. Fluorinating certainpolysiloxanes monomers is known to improve deposit resistance. See, forexample, U.S. Pat. Nos. 4,440,918, 4,990,582, 4,954,587, 5,079,319 and5,010,141.

[0005] Fluorinated polysiloxanes with useful properties for non-hydrogelcontact lenses are disclosed in U.S. Pat. Nos. 4,810,764 and 5,142,009.It would be desirable to provide a hydrogel material containingfluorinated polysiloxanes that is useful as an ophthalmic lens material.

SUMMARY OF THE INVENTION

[0006] The present invention provides biocompatible materials based onvinyl carbonate endcapped polysiloxanes containing perfluorinated sidechains. The vinyl carbonate endcapped siloxanes are preferablycopolymerized with a hydrophilic comonomer such as N-vinylpyrrolidinone, resulting in transparent, low modulus hydrogelspossessing good properties for lens applications, including high oxygenpermeability and good on-eye movement.

DETAILED DESCRIPTION OF THE INVENTION

[0007] This invention provides vinyl carbonate endcapped fluoro siloxanemonomers and polymeric hydrogel materials useful as biocompatiblematerials. The term “biomaterial” as used herein means a material thatcan be used in long-term contact with bodily tissues. Uses forbiomaterials, in addition to contact lenses and intraocular lenses,include implants, stents, catheters, and the like.

[0008] As used herein, the term “side chain” refers to any chainbranching from the silicone atom of a siloxane group, and may be a sidechain on the silicone atom in a polymeric structure composed of apolysiloxane backbone, especially a polydimethylsiloxane backbone.

[0009] The “terminal” carbon atom of a side chain refers to the carbonatom located at a position furthest from the siloxane group to which thefluorinated side chain is attached. The siloxanes of the invention areendcapped with vinyl carbonate groups. The term “endcapped” means thatthe vinyl carbonate groups are attached to the carbon atom locatedfurthest from the siloxane group to which the fluorinated group isattached. Typically, the polysiloxane polymers are endcapped with vinylcarbonate radicals at terminal ends of the polysiloxane backbone of thepolymeric structure.

[0010] It is preferred in the present invention to place the polarfluorinated group, —(CF₂)_(z)H, at the end of a side chain attached to asiloxane-containing monomer to enhance the solubility of the siloxanemonomer in hydrophilic monomers, such as NVP. When the hydrogen atom inthe terminal fluorinated carbon atom is replaced with a fluoro group,the siloxane-containing monomer is significantly less soluble, or notsoluble at all in the hydrophilic comonomer.

[0011] In one embodiment of the present invention, fluorinatedsiloxane-containing monomers are disclosed having at least onefluorinated side chain, said side chain having the general Formula (I):

-D-(CF₂)_(z)H

[0012] wherein z is 1 to 20; and

[0013] D is an alkylene group having 1 to 10 carbon atoms and which mayhave ether (—O—), carbonate (—OCOO—), carbamate (—NHCOO—), ester (—COO—)or amide (—CONH—) linkages between carbon atoms.

[0014] In a further embodiment, the fluorinated siloxane-containingmonomers are based on polydimethylsiloxanes having at least onefluorinated side chain, and contain a moiety of the following generalFormula (II):

[0015] wherein D and z are as previously defined;

[0016] x is ≦0; and

[0017] y is ≦1.

[0018] More preferred are the fluorinated siloxane-containing monomershaving the following general Formula (III):

[0019] wherein:

[0020] each R is independently an alkylene group having 1 to 10 carbonatoms which may have ether linkages between carbon atoms;

[0021] each R′ is independently a monovalent hydrocarbon radical or ahalogen substituted monovalent hydrocarbon radical having 1 to 18 carbonatoms which may have ether linkages between carbon atoms;

[0022] each R³ is hydrogen or methyl

[0023] w and x are each ≧0;

[0024] y is ≧1;

[0025] w+x+y=2 to 1000, more preferably 25 to 200; and

[0026] R″ is the fluorinated side chain, preferably a side chain ofFormula (I)

-D-(CF₂)_(z)—H

[0027] wherein D and z are as previously defined.

[0028] One especially preferred fluorinated side chain is represented bythe formula:

—CH₂—CH₂—CH₂—O—CH₂—(CF₂)_(z)—H

[0029] where z is 1 to 20, preferably 4.

[0030] The fluorinated polysiloxane-containing monomers of the presentinvention combine the desirable features of known hydrophilic side chainpolysiloxanes, such as relative compatibility with hydrophilic monomers,with improved deposit resistance from the fluorinated group. Desiredproperties of the lenses may be affected and controlled. For example, byaltering the relative ratio of the comonomers (the aforementionedfluorinated polysiloxane monomer to the hydrophilic monomer ormonomers), certain hydrogel characteristics in the polymerizedfluorinated polysiloxane copolymer may be altered.

[0031] The relative softness or hardness of the contact lensesfabricated from the resulting polymers of this invention can be variedby decreasing or increasing the molecular weight of the polysiloxanemonomer endcapped with the activated unsaturated group or by varying thepercent of the comonomers present. Generally, as the ratio ofpolysiloxane units to end-cap units increases, the softness of thematerial increases.

[0032] The present invention contemplates the use of the fluorinatedpolysiloxane monomer for both “hard” and “soft” contact lenses, thedisclosed formulations are thought to be especially useful as “soft”hydrogel contact lenses. A lens is considered to be “soft” if it can befolded back upon itself without breaking.

[0033] Especially preferred are hydrogel copolymers. A hydrogel is ahydrated cross-linked polymeric system that contains water in anequilibrium state. Silicone hydrogels (i.e., hydrogels containing asilicone-containing monomer) are usually prepared by polymerizing amixture of lens-forming monomers including at least onesilicone-containing monomer and at least one hydrophilic monomer. Eitherthe silicone-containing monomer of the present invention may function asa crosslinking agent, a crosslinking agent being defined as a monomericmaterial having multiple polymerizable functionalities, oralternatively, a separate crosslinking monomer may be employed.

[0034] Preferred hydrophilic comonomers include N-vinyl pyrrolidinone(NVP), N-vinylacetamide, N-vinyl-N-methyl acetamide, N-vinyl-N-ethylacetamide, N-vinylformamide, N-vinyl-N-ethyl formamide,N-vinylformamide, 2-hydroxyethyl-vinyl carbonate, and2-hydroxyethyl-vinyl carbamate (beta-alanine), with NVP being the mostpreferred.

[0035] For silicone hydrogels, the lens-forming monomer mixture mayfurther include, in addition to the monomer of this invention and thehydrophilic monomer, an additional silicone-containing monomer. Onepreferred class of lens-forming silicone-containing monomers are knownbulky, monofunctional polysiloxanylalkyl monomers represented by Formula(IV):

[0036] where X denotes —OCOO—, or —OCONR⁴— where each R⁴ is H or loweralkyl; R³ denotes hydrogen or methyl; h is 1 to 10; and each R²independently denotes a lower alkyl or halogenated alkyl radical, aphenyl radical or a radical of the formula —Si(R⁵)₃ wherein each R⁵ isindependently a lower alkyl radical or a phenyl radical. Such bulkymonomers specifically include 3-[tris(trimethylsiloxy)silyl] propylvinyl carbamate, and 3-[tris(trimethylsiloxy)silyl] propyl vinylcarbonate. These monomers are further described in U.S. Pat. No.5,070,215 (Bambury et al.).

[0037] Another class of lens-forming silicone-containing monomers arethose represented by Formula (V):

[0038] where:

[0039] X denotes —OCOO—, or —OCONR⁴— where each R⁴ is H or lower alkyl;

[0040] each R denotes an alkylene or haloalkylene group having 1 to 10carbon atoms and which may have ether linkages between carbon atoms;

[0041] each R′ is independently a monovalent hydrocarbon radical or ahalogen substituted monovalent hydrocarbon radical having 1 to 18 carbonatoms which may have ether linkages between carbon atoms;

[0042] each R³ is hydrogen or methyl; and

[0043] w is ≧0.

[0044] Specific examples include: 1,3-bis (4-vinyloxycarbonyloxy)but-1-yl)tetramethyl-disiloxane; wherein in Formula IV, w is about 25,each X—OCOO—, each R³ is methyl, each R is butylene; and each R′ ismethyl. These monomeric materials are further described in U.S. Pat. No.5,070,215.

[0045] The relative ratio (wt. %) of siloxane-containing monomer tototal wt. % of comonomer mixture is preferably from about 10% to about85%, more preferably from about 20% to about 70%, and most preferablyfrom about 25% to about 40%. The relative ratio (wt. %) of hydrophilicmonomer(s) to total wt. % of the comonomer mixture is preferably fromabout 20% to about 90%, more preferably from about 30% to about 80%, andmost preferably from about 50% to about 60%.

[0046] Accordingly, for lens applications, the monomer mixtures employedin the invention include a monomeric material of this invention mixedwith various conventional lens-forming monomers. All the lens-formingmonomers are monomers that are polymerizable by free radicalpolymerization, generally including an activated unsaturated radical,and most preferably an ethylenically unsaturated radical. As usedherein, the term “monomer” and like terms denote relatively lowmolecular weight compounds that are polymerizable by free radicalpolymerization, as well as higher molecular weight compounds alsoreferred to as “prepolymers”, “macromonomers”, and similar terms.Optionally, the initial monomeric mixture may also include additionalmaterials such as solvents, colorants, toughening agents, UV-absorbingagents and other materials such as those known in the contact lens art.Representative solvents are disclosed in U.S. Pat. Nos. 5,260,000 (Nanduet al.) and 6,020,445 (Vanderlaan et al.).

[0047] The instant copolymers can be readily cured to cast shapes byconventional free radical polymerization methods where the monomericmixture is exposed to light radiation, such as visible light or UVradiation, to heat, or both, to induce polymerization. Representativefree radical thermal polymerization initiators are organic peroxides,such as acetal peroxide, lauroyl peroxide, decanoyl peroxide, stearoylperoxide, benzoyl peroxide tertiarybutyl peroxypivalate,peroxydicarbonate, and the like, employed in a concentration of about0.01 to 1 percent by weight of the total monomer mixture. RepresentativeUV initiators are those known in the field such as, benzoin methylether, benzoin ethyl ether, and those initiators available under thetradenames Darocure 1173, 1164, 2273, 1116, 2959, 3331 (EM Industries)and Igracure 651 and 184 (Ciba-Geigy).

[0048] According to various preferred embodiments, these hydrogelmaterials are suitable for biomedical applications. The terms “shapedarticles for use in biomedical applications” or “biomedical devices ormaterials” mean the hydrogel materials disclosed herein havephysicochemical properties rendering them suitable for prolonged contactwith living tissue, blood and the mucous membranes.

[0049] Generally, the monomer mixtures may be charged to a mold, andthen subjected to the light radiation or heat to effect curing of themonomer mixture in the mold. Various processes are known for curing amonomeric mixture in the production of contact lenses, includingspincasting and static casting. Spincasting methods involve charging themonomer mixture to a mold, and spinning the mold in a controlled mannerwhile exposing the monomer mixture to light. Static casting methodsinvolve charging the monomer mixture between two mold sections, one moldsection shaped to form the anterior lens surface and the other moldsection shaped to form the posterior lens surface, and curing themonomer mixture by exposure to light. Such methods are described in U.S.Pat. Nos. 3,408,429, 3,660,545, 4,113,224, 4,197,266, and 5,271,875.Additionally, the monomer mixtures may be cast in the shape of rods orbuttons, which are then lathe cut into a desired lens shape.

[0050] The hydrogels produced by the present invention are oxygentransporting, hydrolytically stable, biologically inert, andtransparent. The monomers and copolymers employed in accordance withthis invention are readily polymerized to form three-dimensionalnetworks which permit the transport of oxygen and are optically clear,strong and hydrophilic.

[0051] The present invention further provides articles of manufacturewhich can be used for biomedical devices, such as, surgical devices,heart valves, vessel substitutes, intrauterine devices, membranes andother films, diaphragms, surgical implants, blood vessels, artificialureters, artificial breast tissue and membranes intended to come intocontact with body fluid outside of the body, e.g., membranes for kidneydialysis and heart/lung machines and the like, catheters, mouth guards,denture liners, intraocular devices, and especially contact lenses.

[0052] The following examples serve only to further illustrate aspectsof the present invention and should not be construed as limiting theinvention.

EXAMPLE 1-5

[0053] The vinyl carbonate endcapped polysiloxanes containingperfluorinated side chains of the present invention may be preparedaccording to the following general reaction scheme.

[0054] First, a cyclic siloxane tetramer, containing the perfluorinatedside chain, is prepared according to Scheme I:

[0055] Next, the vinyl carbonate endcapped siloxanes are prepared by anacid catalyzed ring opening polymerization of this fluorinated cyclicsiloxane tetramer (and optionally octamethylcyclotetrasiloxane) using adivinyl carbonate endcapped disiloxane, as shown in Scheme II:

[0056] The activated resin employed in Scheme II is preferably preparedby placing amberlyst-15 resin (100 g) in a 1000-ml Erlenmeyer flask with500 ml of THF. This mixture is stirred for 18 hours, then the resin isfiltered off and allowed to air dry. Next, the recovered resin is placedin a 1000-ml Erlenmeyer flask with 400 ml of 0.1N HCl. This mixture isstirred for 3 hours and the acid is decanted. The resin is washed withdistilled water until a neutral pH is obtained, and this resin is thendried.

[0057] To prepare the prepolymer in Scheme II, the dried resin is mixedwith distilled water, and to this mixture is added the fluorinatedcyclic siloxane tetramer, the divinyl carbonate endcapped disiloxane,and optionally, the octamethylcyclotetrasiloxane shown in Scheme II.When the octamethylcyclotetrasiloxane is employed in the reactionmixture, the molar ratio of the fluorinated cyclic siloxane tetramer andoctamethylcyclotetrasiloxane is selected to obtain prepolymers havingthe desired x and y values in the following Formula (II) moiety of theprepolymers:

[0058] The amount of the divinyl carbonate endcapped disiloxane ofScheme II is selected based on the desired total siloxane chain length,i.e., (x+y) in Formula II above. Prepolymers with other flourinated sidechains can be prepared similarly by employing cyclic siloxane tetramerswith the desired side chain.

[0059] Following this procedure of Scheme II, the prepolymer of Example1 was prepared by first mixing 10.0 g of the dried resin with 1.0 g ofdistilled water in a 3-neck round bottom flask. To this mixture wasadded the fluorinated cyclic siloxane tetramer (97.05 g), and thedivinyl carbonate endcapped disiloxane (2.95 g). This reaction mixturewas stirred for several days at room temperature, then filtered toremove the amberlyst resin. The final reaction product was a clearviscous fluid. The prepolymers of Examples 2 to 5, shown in Table 1,were prepared similarly. Each of the prepolymers in Table 1 areprepolymers of Formula (III), where each R is butylene, each R′ ismethyl, and R″ is the side chain —(CH₂)₃—OCH₂—CF₂)₄H. TABLE 1 Example xy 1 75 25 2 112.5 37.5 3 135 15 4 142.5 7.5 5 90 10

EXAMPLES 6-57

[0060] A series of monomer mixtures, suitable for providing siliconehydrogel contact lenses copolymeric materials, were prepared by mixingthe components in Tables 2-6. The solvent employed in these mixtures was3,7-dimethyl-3-octanol. In these following tables, NVP denotes thehydrophilic monomer N-vinyl pyrrolidinone, and TrisVC denotes themonofunctional polysiloxanylalkyl comonomer3-[tris(trimethylsiloxy)silyl] propyl vinyl carbamate. Additionally,these monomer mixtures included 0.5 parts by weight (pbw) of theinitiator Darocure-1173. The amounts listed in Tables 2-6 are parts byweight.

[0061] These monomer mixtures were cured between two silane-treatedglass plates under an ultraviolet (UV) light source with an intensity of300 microwatts for about 2 hours. The cured films were then released,extracted in isopropanol and dried overnight. The dried films weresoaked and hydrated in a borate buffered saline solution overnightbefore characterization. Tensile tests were performed in borate bufferedsaline according to ASTM D-1708. The results are set forth in Table 1where modulus is reported in units of g/mm², tear strength is reportedin units of g/mm, and Dk is reported in units of Barrer. TABLE 2Prepolymer % Ex of Ex 1 Solvent TrisVC NVP Modulus Tear Dk Water 6 3011.3 65 33 64 29 109.6 23.8 7 30 17.3 65 27 92 33 120.9 21.5 8 30 17.365 27 83 39 130.7 22.9 9 30 20.6 55.6 33 59 26 83.0 30.0 10 30 30 49.330 47 21 85.9 35.2 11 30.6 30 45.6 33 46 19 80.8 35.3 12 37.3 30 45 2746 19 99.3 32.2 13 40.6 20.6 45 33 49 13 79.9 31.1 14 40.8 15.8 55.8 2765 24 128.0 23.0 15 44.3 0 65 30 70 23 125.6 22.8 16 50 0 56.3 33 65 1493.5 28.0 17 50 0 56.3 33 58 15 112.4 26.2 18 50 0 62.3 27 65 18 94.020.0 19 50 8.6 53.6 27 60 17 123.5 19.2 20 50 11.3 45 33 60 12 108.027.0 21 21.5 12.4 46.5 19.31 97 40 124.7 26.9 22 18.6 0 63 18 213 73147.6 25.0 23 35.8 12.4 32.2 19.31 61 11 133.6 24.7 24 18.6 0 63 18 22871 160.6 —

[0062] TABLE 3 Prepolymer % Ex of Ex 2 Solvent TrisVC NVP Modulus TearDk Water 25 30 14.3 65 30 57 40 83.3 29.0 26 30 20.6 55.6 33 113 29 77.336.3 27 40.6 20.6 45 33 45 19 82.7 33.7 28 40.8 15.8 55.8 27 66 34 116.127.2 29 50 11.3 45 33 56 16 95.8 30.8 30 40 20 55 30 58 21 — 26.9

[0063] TABLE 4 Prepolymer Ex of Ex 3 Solvent TrisVC NVP Modulus Tear 3130 14.3 65 30 — — 32 30 20.6 55.6 33 — — 33 40.6 20.6 45 33 — — 34 40.815.8 55.8 27 44 19 35 50 11.3 45 33 49 12 36 40 20 55 30 43 19

[0064] TABLE 5 Prepolymer Ex of Ex 4 Solvent TrisVC NVP Modulus Tear 3730 14.3 65 30 49 28 38 30 20.6 55.6 33 41 17 39 40.6 20.6 45 33 34 13 4040.8 15.8 55.8 27 — — 41 50 11.3 45 33 — — 42 40 20 55 30 — —

[0065] TABLE 6 Prepolymer % Ex of Ex 5 Solvent TrisVC NVP Modulus TearDk Water 43 30 14.3 65 30 51 23 184.5 23.6 44 30 20.6 55.6 33 48 18111.7 28.3 45 30 30 52.3 27 41 19 109.2 26.8 46 30 30 52.3 27 40 17126.5 30.5 47 34.3 30 45 30 44 13 104.7 30.6 48 38.6 8.6 65 27 59 17148.4 19.5 49 40.6 20.6 45 33 62 10 100.8 25.8 50 40.8 15.8 55.8 27 6015 154.5 23.2 51 41.3 0 65 33 57 15 146.5 24.3 52 41.3 0 65 33 55 14100.3 23.4 53 48.6 0 63.6 27 63 13 141.1 19.5 54 50 7.2 52.2 30 70 10149.2 21.9 55 50 11.3 45 33 69 9 151 26.2 56 50 17.3 45 27 68 7 116.634.8 57 50 17.3 45 27 74 10 172.8 20.8

EXAMPLE 58

[0066] Various monomer mixtures in Tables 2-6 may be used to castcontact lenses. The monomer mixture is placed on the molding surface ofa first plastic mold section, shaped to provide an anterior contact lenssurface, and a second plastic mold section having a molding surfaceshaped to provide a posterior contact lens surface, the monomer mixturebeing contained in the mold cavity formed between these two moldingsurfaces. This assembly is subjected to a UV light source to cure themonomer mixture. Following curing, the two mold sections are separatedto recover the contact lens.

[0067] Many other modifications and variations of the present inventionare possible to killed practitioner in the field in light of theteachings herein. It is therefore stood that, within the scope of theclaims, the present invention can be practiced than as hereinspecifically described.

We claim:
 1. A hydrogel that is the hydrated polymerization product of amonomer mixture comprising a hydrophilic monomer, and a monomer of theformula:

wherein: each R is independently an alkylene group having 1 to 10 carbonatoms which may have ether linkages between carbon atoms; each R′ isindependently a monovalent hydrocarbon radical or a halogen substitutedmonovalent hydrocarbon radical having 1 to 18 carbon atoms which mayhave ether linkages between carbon atoms; each R³ is hydrogen or methylw and x are each ≧0; y is ≧1; w+x+y=2 to 1000; and R″ is a fluorinatedside chain of the formula -D-(CF₂)_(z)—H, wherein z is 1 to 20, and D isan alkylene group having 1 to 10 carbon atoms which may have ether,carbonate, carbamate, ester or amide linkages between carbon atoms. 2.The hydrogel of claim 1, wherein said monomer mixture further comprisesa monofunctional polysiloxanylalkyl monomer.
 3. The hydrogel of claim 2,wherein the monofunctional polysiloxanylalkyl monomer is represented bythe formula:

wherein: X denotes —OCOO—, or —OCONR⁴— where each R⁴ is H or loweralkyl; R³ denotes hydrogen or methyl; h is 1 to 10; and each R²independently denotes a lower alkyl or halogenated alkyl radical, aphenyl radical or a radical of the formula —Si(R⁵)₃ wherein each R⁵ isindependently a lower alkyl radical or a phenyl radical.
 4. The hydrogelof claim 3, wherein the monofunctional polysiloxanylalkyl monomer isselected from the group consisting of 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate and 3-[tris(trimethylsiloxy)silyl] propyl vinylcarbonate.
 5. The hydrogel of claim 1, wherein said hydrophilic monomeris selected from the group consisting of N-vinyl-N-methyl acetamide,N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl-formamide,N-vinyl pyrrolidone, and mixtures thereof.
 6. The hydrogel of claim 5,wherein the hydrophilic monomer includes N-vinyl pyrrolidinone.
 7. Thehydrogel of claim 1, wherein R″ is —CH₂—CH₂—CH₂—O—CH₂—(CF₂)₄—H.
 8. Acontact lens made from the polymerization product of a monomer mixturewhich comprises a vinyl carbonate endcapped polysiloxane containing afluorinated side chain.
 9. The contact lens of claim 8, wherein thevinyl carbonate endcapped polysiloxane is of the formula:

wherein: each R is independently an alkylene group having 1 to 10 carbonatoms which may have ether linkages between carbon atoms; each R′ isindependently a monovalent hydrocarbon radical or a halogen substitutedmonovalent hydrocarbon radical having 1 to 18 carbon atoms which mayhave ether linkages between carbon atoms; each R³ is hydrogen or methylw and x are each ≧0; y is ≧1; w+x+y=2 to 1000; and R″ is a fluorinatedside chain of the formula -D-(CF₂)_(z)—H, wherein z is 1 to 20, and D isan alkylene group having 1 to 10 carbon atoms which may have ether,carbonate, carbamate, ester or amide linkages between carbon atoms. 10.The contact lens of claim 9, wherein the monomer mixture furthercomprises a hydrophilic monomer.
 11. The contact lens of claim 10,wherein said hydrophilic monomer is selected from the group consistingof N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide,N-vinyl-N-ethyl formamide, N-vinyl-formamide, N-vinyl pyrrolidone, andmixtures thereof.
 12. The contact lens of claim 11 wherein thehydrophilic monomer includes N-vinyl pyrrolidinone.
 13. The contact lensof claim 10, wherein said monomer mixture further comprises amonofunctional polysiloxanylalkyl monomer.
 14. The contact lens of claim13, wherein the monofunctional polysiloxanylalkyl monomer is representedby the formula:

wherein: X denotes —OCOO—, or —OCONR⁴— where each R⁴ is H or loweralkyl; R³ denotes hydrogen or methyl; h is 1 to 10; and each R²independently denotes a lower alkyl or halogenated alkyl radical, aphenyl radical or a radical of the formula —Si(R⁵)₃ wherein each R⁵ isindependently a lower alkyl radical or a phenyl radical.
 15. The contactlens of claim 14, wherein the monofunctional polysiloxanylalkyl monomeris selected from the group consisting of 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate and 3-[tris(trimethylsiloxy)silyl] propyl vinylcarbonate.
 16. The contact lens of claim 10, wherein R″ is—CH₂—CH₂—CH₂—O—CH₂—(CF₂)₄—H.
 17. A monomer of the formula: wherein:

each R is independently an alkylene group having 1 to 10 carbon atomswhich may have ether linkages between carbon atoms; each R′ isindependently a monovalent hydrocarbon radical or a halogen substitutedmonovalent hydrocarbon radical having 1 to 18 carbon atoms which mayhave ether linkages between carbon atoms; each R³ is hydrogen or methylw and x are each ≧0; y is ≧1; w+x+y=2 to 1000; and R″ is a fluorinatedside chain of the formula -D-(CF₂)_(z)—H, wherein z is 1 to 20, and D isan alkylene group having 1 to 10 carbon atoms which may have ether,carbonate, carbamate, ester or amide linkages between carbon atoms. 18.The monomer of claim 17, wherein w+x+y 25 to
 200. 19. The monomer ofclaim 17, wherein D is an alkylene group having 1 to 10 carbon atomswhich may have ether, linkages between carbon atoms